Process of purifying pinene hydrochlorid.



No. 747,629. Patented December 22, 1903.

UNITED STATES PATENT OFFICE.

WILHELM NASCHOLD, OF UERDINGEN, GERMANY, ASSIGNOR OF ONE-HALF TO THE FIRM OHEMISCHE FABRIK UERDINGEN LIENAU AND 00., OF UERDINGEN, GERMANY.

PROCESS OF PURIFYING PINENE HY'DROCHLORID.

SPECIFICATION formingpart of Letters Patent No. 747,629, dated December 22, 1903.

Application filed October 16.11902. Serial No. 127,5 79- (No specimens.)

To all whom it may concern: chloric acids, which are inherent in the for Be it known that I, WILHELM NASCHOLD, mation of pinene hydrochlorid and which are doctor of philosophy, a subject of the German the cause of the defective keeping qualities Emperor,residingatUefllingen-on-the-Rhine, of the product, may be removed by careful Kingdom of Prussia, German Empire,'have saponification. In accordance with this dis- 5 invented new and useful Improvements in covery the present process consists in sub Processes of Purifying Pinene Hydrochlorid, mitting' raw or, if desired, preliminarily-puriof which the following is a specification. fied pinene hydrochlorid to the action of My invention relates to .the processes of saponifying agents, the condition being, howlo'purifying pinene hydrochlorid, and has for ever, observed that only the subproducts its object to render the pinene hydrochlorid shall be decomposed and this quite or pracmore stable and more suitable for technical tically completely, while the pinene hydro use, especially as a substitute for eamphor. chlorid remains practically unattacked. In

The technical employment of pinene hydroorder to prove that the pinene hydrochlorid I5 chlorid, (O H CQ) otherwise termed hydrois not attacked to any extent, simple experichloric turpentine spirit or artificial camments may be made with pure material. If phor, has hitherto mainly failed, because the another purifying process is carried out, it product as heretofore manufactured will not is sufficient to continue the saponification remain neutral for any length of time unless until the final product no longer exhibits 2o toocostlyanddisadvantageouspurifying procany unsaponified particles. esses are resorted to-such, for example, as In carrying out the process described above repeated recrystallization from alcohol. The known saponifying agents may be employed. formation of acids when pinene hydrochlorid First among these come water, dilute acids, manufactured in the known manner is stored alkalies, alkaline earths, and carbonates of 25 is caused,in the first place,"by the presence of the alkalies and alkaline earths. The temby-products, which are ordinarily formed in perature should preferably be so high that the process, which readily liberate hydrothe raw pinene hydrochlorid is completely chloric acid, while pinene hydrochlorid itself liquefied. Atlower temperatures the saponiis a comparatively permanent substance, fication may readily be incomplete or it may 30 which in considerable degree can only be deoccupy too long a time. A suitable tempera- 8o composed at high temperatures and by ener- .ture is from to 100 centigrade, and the getically-acting agents. The frequently-reaction is facilitated by intimate mixing by peated proposition to produce a practical means of an agitator or the like mechanism. preparation by neutralizing with alkalies the Owing to the volatility of the product, it is 35 free acids which are present, followed by dispreferable to employ closed vessels. The tillation or sublimation, has not'att ained the quantitive proportions to be employed vary desired end, because by this means only the according to the properties of the raw prodfree acids which are present at the time the not and must be determined for each case by treatment takes place can be removed, while the expert operator. The termination of the 40 the formation of free hydrochloric acid by operation may, for example, be recognized, 0 the decomposition of the subproducts when owing to the fact that a sample boiledwith the substance is stored can obviously only be dilute alcohol free from acid will no longer partially and inefficiently prevented in such yield any considerable quantity of free'acid.

a manner. It is, however, better to determine the saponi- 5 The process which forms the subject of fying number in the usual manner with a 5 this invention has for its object the producsample which is not too small and compare it tion of a pinene hydrochlorid which remains with that of pure pinene hydrochlorid, which neutral when the substance is stored and is may be ascertained under like conditions of based upon the novel observation that the saponification once for all. Pure pinene hy-- 5o subproducts which readily liberate hydrodrochlorid is itself not absolutely invariable I00 under the usual conditions for fixing the sapouifying number, but is gradually decomposed to a small extent. There is therefore a certain, although only a very small, consumption of alkali, which is dependent upon the conditions of experiment and which should not be neglected in exact operations.

Example: Five grams pure pinene hydrochlorid recrystallized many times from alcohol is boiled at a reflux cooler for thirty minutes in a water-bath with a measured quantityof standard soda or potash lye free from carbonic acid and a quantity of alcohol sufficient forcausing solution, then cooled and dilutedwith a proportionatequantity of pure waterfree from carbonic acid and titrated back withstandard acid, phenolphtalein being employed as indicator. From the consumption of standard alkali, is calculated in the usual manner the saponifying number of pure pinene hydrochlorid proper for the selected experimental conditions. Thereupon the sapouifying number for the product to be treated may be exactly determined under like conditions. From the found saponifying number may be calculated the quantity of sodium carbonate solution of the desired concentration necessary for saponification. There is then introduced into a boiler'provided with aheating-jacketefiicient agitating mechanism and a gas-discharge circuit and which is adapted to be closed, a weighed quantity of the raw product and somewhat more than the calculated quantity of sodium-carbonate solution. The mixture is then heated to about 80 to 100 and stirred untila sample taken out and freed from soda by washing and treated in a centrifugal machine does not give a higher saponifying number than pure pinene hydrochlorid. When this point is reached, the mixture is allowed to stand and the product is separated and washed in the usual manner. The product obtained in this manner will, if carefully stored, retain its natural reaction foralongperiod. Adefect in the product obtained in this manner consists in the fact that it contains considerable quantities of oily substances, which lower the melting-point and prej udically affect the technical utility. The removal of the oily substances by distillation, sublimation, or mechanical separation is not satisfactory, as, on the one hand, the boiling-point and the volatility of the oil differ only slightly from those of the main product,while, on the other hand, great mutual solubility of the pinene hydrochlorid and the oils is present. While, therefore, the method described employed alone cause considerable loss of pure material, it has been found that the separation of the oily subproducts by distilling the pinene hydrochlorid with steam and sublimation is almost a complete success and gives a good yield of pinene hydrochlorid if the oily substances are chemically altered in a suitable manner so that their volatility, either alone or with steam, becomes very small. Such an alteration may be obtained owing to the fact, which has been observed, that the said oily substances are organic compounds of small stability, which by means of vigorously-acting agents known for this purpose, especially those of an acid character, readily undergo an almost complete resinification. In elfecting such resinification care must again be taken that the conditions are such that any appreciable action of the medium employed upon the pinene hydrochlorid will not take place. Concentrated sulfuric acid has shown itself peculiarly suited for the separation of the oily subproducts. Contrary to most com pounds of the terpene group, pinene hydrochlorid strongly resists concentrated sulfuric acid and is practically insoluble therein at ordinary and even at moderately higher temperatures. The oily subproducts, on the other hand, are for the greater part dissolved by the acid and resinified under like conditions. It is therefore permissible to employ concentrated sulfuric acid as resinifying agent for the purpose in view and at the same time it is possible to remove the greater part of the subproducts by mechanical separation, while the resinification process described above does not necessitate any subsequent distillation or sublimation.

Example I: The saponified product or the oily constituents separated therefrom in any convenient manner are heated with sulfuric acid of, say, 1.5 specific weight and while stirring to a temperature of 80 to 100 centigrade. The duration of the reaction depends upon the proportion of oil in the prodnet, the quantity and concentration of the acid, and the intimacy of the mixing and may be readily determined by simple experiment. Thereupou the product separated from the acid is neutralized with sodium carbonate and distilled with steam.

Example II: The pinene hydrochlorid treated with saponifying agents in the manner above described is mixed with about the same volume of concentrated sulfuric acid, any considerable heating being avoided, and the mixture is poured upon ice and distilled with steam.

Example III: Raw pinene hydrochlorid is freed from readily-saponified constituents by treatment with a soda solution in the mannerindicated above. It is then separated from the aqueous solution and after cooling submitted to centrifugal treatment. The crystalline mass thus obtained is stirred with concentrated sulfuric acid into a thick paste two or three times and treated in a centrifugal machine, the acid coming from the purer products being systematically used for stirring with products of less purity. The product is then covered with water, neutralized by mixing with a sodium-carbonate solution, again treated in a centrifugal machine, and finally distilled with steam.

The resinification of the oily constituents may be combined with the saponification by eflfecting the two operations simultaneously. The resinifying mediumsulfuric acid, for examplethen acts upon the raw product employed in such a manner as to saponify and resinify at the same time. The unification of the operations carries with it a disadvan- 'tage, however, inasmuch as owing to the unavoidable presence of free hydrochloric acid the apparatus employed is readily attacked. In most cases it is therefore preferable to maintain the reaction mixture alkaline or neutral for the saponification and to effect the resinification of the oils separately by means of sulfuric acid. In any case when it is desired to obtain a pure white product having a high-melting point further'purification in accordance with known methods, such as distillation, sublimation, or the like, may be carried out. The pinene hydrochlorid purified in this manner is much better adapted for keeping than the products hitherto readily obtainable by technical means heretofore known, and more particularly it does not liberate any hydrochloric acid when kept. This product may, however, undergo a marked acid reaction if it is kept for any considerable time in the air or light or in the presence of moisture. This acid reaction is not, we have discovered, attributable to hydrochloric acid, but apparently to traces of organic acids which, under the influence of the oxygen in the atmosphere, are produced from small quantities of adherent subproducts. If, for example, a preparation which has become acid in this manner after a considerable lapse of time is washed in a little water, the aqueous extract will redden litmus, but not methyl-orange, and with nitrate of silver there is no precipitate:

It may be desired to impart to the pinene hydrochlorid,by the removal of the last traces of subproducts, such a degree of purity that it will retain its neutral reaction even under the influences above referred to. Of the known processes the only one which is suitable for such a purpose is that of crystallization from alcohol, which upon a large scale is bothinconvenient andcostly. Thenumerous methods proposed for distillation with steam and sublimation have proved wanting. It is essential in carrying out those processes that pinene hydrochlorid, together with water, should be heated for a long time to 100, or alone to even higher temperatures. Now we have found that contrary to the known data as to the permanence of pinene hydrochlorid this substance in a pure condition is liable even at about 120 to 130 to the formation of traces of hydrochloric acid and oily substances. In the presence of Water a slight but not inappreciable decomposition takes place even at 100. The hydrochloric acid may be removed in the usual manner, but the traces of oily substances adhere obstinately to the main product and cause it to undergo an acid reaction, as already stated." The said processes therefore of themselves the pinenehydrochlorid is completely freed from water and then is driven over in a comparatively short time at temperatures of not more than 50 to 100. It is true that even under these conditions it does not appear to be absolutely invariable, but the decomposition taking place under these circumstances is so exceedingly small as not to be appreciable during the time necessary for sublimation. The smaller the pressure the lower will be the sublimation temperature, and so much the less change will there be of the formation of decomposition products. It is therefore advantageous to operate with as complete a vacuum as possible. In carrying out the sublimation regard must be had to the hitherto undescribed fact that pinene hydrochlorid is gradually decomposed even at temperatures of 100 and under by many metals, such as zinc and iron. The decomposition proceeds fairly rapidly once it has set in and is especially noticeable when the metals are slightly oxidized. It may be retarded by the addition of small quantities of alkaline agents, such as soda. Furthermore, those parts of the apparatus which come into contact with the pinene hydrochlorid at high temperatures may be formed of such materials as shall have been found by preliminary experiment to be fit. It may be advisable to repeat the sublimation for a second or greater number of times and to keep the first and last products separate.

Preparations of a high degree of impurity, and especially resinified preparations, should preferably be submitted to an ordinary purifying process, such as distillation with steam,

before sublimation.

only the readily-saponified subproducts, and

with a resinifying agent in such a manner as to react only upon the oily subproducts with the said pinene hydrochlorid.

3. The herein-described process for preparing pinene hydrochlorid keeping itself in the neutral state, which consists in treating ordinary pinene hydrochlorid with a saponifying agent and with a resinifying agent in such a manner as to react only with the subproducts present, then subjecting the purified pinene hydrochlorid to sublimation under reduced pressure.

4. The herein-described process for preparing pinene hydrochlorid keepingitself in the neutral state, which consists in treating ordinary pinene hydrochlorid with sodium-carbonate solution in such a manner as to split up only the readily-saponified subprod ucts associated with the said pinene hydrochlorid.

5. The herein-described process for preparing pinene hydrochlorid keeping itself in the neutral state, which consists in treating ordinary pinene hydrochlorid with sodium-carbonate solution in such a manner as to split up only the readily-saponified subproducts and with sulfuric acid in such a manner as to resinify only the oily subproducts associated with the said pinene hydrochlorid.

6. The herein-described process for preparing pinene hydrochlorid keeping itself in the neutral state, which consists in treating ordinary pinene hydrochlorid with sodium carbonate and with sulfuric acid in such a manner as to react only with the subproducts present, then subjecting the purified pinene hydrochlorid to sublimation under reduced pressure.

In Witness whereof I have hereunto signed my name, this 6th day of October, 1902, in

the presence of two subscribing witnesses.

WILHELM NASOHOLD.

Witnesses:

J 0s. MULLER, FRANZ GIEBEL. 

